Agricultural chemical compositions



United States Patent AGRICULTURAL CHEMICAL COMPOSITIONS Gilbert SpencerHartley, Fulbourn, and Roynon Howes,

Saffron Walden, England, assignors to Fisons Pest Control Limited,Harston, England No Drawing. Filed July 14, 1960, Ser. No. 42,777 Claimspriority, application Great Britain July 22, 1959 12 Claims. (Cl. 712.7)

The present invention concerns an improvement in agricultural chemicalcompositions.

In our U.S. Patent No. 2,907,691 is described a composition containingan agricultural chemical which is insoluble or slightly soluble in waterwhich also contains a compound comprising the salt of trimethylamine ortriethylamine and a long chain saturated aliphatic carboxylic acid or anunsaturated aliphatic carboxylic acid with at least two double bonds.These compounds act both as dispersing agent and sticking agent.

It has now been found that where it is desired to spray agriculturalchemicals from a height, such as for example from aircraft, byincorporating the composition a volatile base and a long chain saturatedaliphatic acid, droplets of these compositions can exhibit sufficientlydelayed evaporation to reach the ground in a liquid condition. Themixture of the volatile base and the acid acts also as dispersing agentand sticking agent.

For satisfactory control of evaporation it is necessary that the fattyacids be predominantly saturated. Unsaturated acids like oleic orlinoleic do not have a worthwhile effect and, if present as impuritiesto an extent of more than about 20% of the saturated acids, they reducethe effect of the latter. The effect is also reduced by theincorporation of many well known types of surface active compounds andwhere it is necessary for additional surface active compounds to bepresent to control flocculation, sedimentation etc., compounds where thehydrophilic property is derived from condensed alkylene oxide arepreferred.

It has further been found that products of the type using lower aminessuch as trimethylamine or triethylamine, have undesirable features inpractice. The amine stearate is not present in a true and mobilesolution form, but rather as an extremely finely divided crystallinematerial producing an abnormal viscosity or gel type struc ture in theproduct. The behaviour of the products in this respect is much dependenton the precise way in which they were made up. They are gelatinous ifmade up hot and allowed to cool in a quiescent condition and more mobileif subjected to violent agitation in the cold. Furthermore, the productsbuild very stable foams when agitated in such a way as to incorporateair.

It has now been found that alkylamines and cycloalkylamines of more than6 carbon atoms, form solutions of stearic acid and other fatty acids inwater which have a much reduced tendency to build up a stable froth.Furthermore, some but not all, of these amines form solutions withstearic acid in water which may be cloudy in appearance but aresufficiently mobile when freshly prepared at ordinary temperatures to beeasily sprayable.

Additionally since the higher amine-fatty acid salts or mixtures areusually liquid, and neither highly inflammable nor highly volatile, theformulant can be marketed in this form, whereas the lower amines such astrimethylamine and triethylamine are highly volatile and inflammable andpresent serious inconveniences in use.

In the spraying of agricultural chemicals, and particularly in aerialspraying, it is desirable to minimise the volume of liquid sprayed. Inthe case of many chemicals low volume formulations are not practicableon account of the rapid evaporation of the spray droplets which resultsin the chemical arriving on the crop in a dry form 3,133,809 PatentedMay 19, 1964 but too coarse to be adherent as a dust. The presentinvention provides a composition which on account of its delayedevaporation is capable of being sprayed at low volume rates, for example1-2 gallons per acre.

Accordingly the present invention is for a composition containing anagricultural chemical which also contains an amine of more than 6 carbonatoms, and a long chain saturated aliphatic carboxylic acid.

The compositions according to the present invention may comprise whereappropriate aqueous suspensions or solutions containing the agriculturalchemical and an amine and a long chain aliphatic carboxylic acid asidentified suitably diluted for spraying on to a crop. The compositionsmay also be concentrates for storage and sale which may be in the formof more or less stiff pastes intended to be diluted to spray strength onthe spot. The compositions may even be dry powders prepared by reductionto dryness, if this is possible without decomposition and providing thatthe amine carboxylic acid mixture is not a liquid at normaltemperatures, or by impregnating a suitable absorbent powder. Thecompositions of the invention may of course contain in addition inertdiluents and other compounds common in spray liquids such as suspendingagents, antiflocculants and the like.

Owing to the low viscosity of aqueous solutions of the mixtures of theseamines with the fatty acid, for example stearic acid, in the case ofwater insoluble agricultural chemicals it is not usually practicable tosupply a liquid concentrate since the insoluble agricultural chemicalsediments in storage and, after a considerable period, can only withdifficulty be resuspended.

In such cases therefore, the amine fatty acid mixture is preferablyprovided as a separate liquid concentrate in one pack and theagricultural chemical, for example as a fine powder, in another, to bemixed together with water immediately prior to spraying.

Accordingly a further embodiment of the invention is for a formulant foragricultural chemical compositions which comprise a salt or mixture of afatty acid and an amine or more than 6 carbon atoms.

The agricultural chemical may comprise a fungicide, pesticide,herbicide, plant growth regulant or other chemical used to ensure planthealth, and may be water soluble or water insoluble. However theinvention is of particular advantage in the case of agriculturalchemicals which are insoluble or substantially insoluble in water.According to a preferred embodiment of the invention the agriculturalchemical comprises a fungicidal copper compound such as cuprous oxide orcopper oxychloride. The present invention however is not restricted tosuch compounds and may contain other fungicides such for example as thenickel fungicides, for example nickel hydroxide; the organo sulphurfungicides, for example tetramethylthiuram disulphide and divalent metalsalts, such as zinc and manganese, of ethylene-bis-ditbiocarbamic acid;insecticides such for example as DDT, BHC, sevin (alpha-naphthyl esterof N-methyl carbamic acid), aldrin (l:2:3:4:l0:l0 hexachloro1:4:4a:5:8:8a hexahydro-l:4-endo, exo-S:S-dimethano-naphthalene) anddieldrin (1:2:3:4:10:1O hexachloro 6:7 epoxy 1:4:4a: 5:6:718z8aoctahydro 1:4-endo, exo-5z8-dimethanonaphthylene), bis-N:N:N'N'tetramethylphosphorwdiamidic anhydride, and0,0-dimethyl-S-(N-methyl-carbamoyl-methyl)phosphorodithioate; orherbicides such as N-parachlorophenyl NN' dimethyl-urea, and simazin(2-chloro-4:6-bis-ethyl-amino-triazine); or mixtures of any of the abovetogether with other materials.

The long chain saturated aliphatic carboxylic acid may comprise forexample an acid which is solid at normal temperatures preferablycontaining at least 13 carbon atoms, and for example 14-22 carbon atomsin the chain, such as myristic acid, palmitic acid, arachidic acid,

3 behenic acid and stearic acid. The long chain saturated aliphaticcarboxylic acid is preferably stearic acid. If desired, mixtures of anyof these acids may also be used, and in any event the commercialproducts normally comprise mixtures.

The amines of higher molecular weight suitably comprise amines of morethan 6 carbon atoms. Preferably the amine does not contain more than 16carbon atoms since amines of higher molecular weight than this tend toform two-phase mixtures with fatty acids and water. The amine usedaccording to the present invention suitably comprises tertiary aminessuch as tri-n-propyl, tri-isopropyl, methyldipropyl, methyldiallyl,methyldibutyl, methyldiamyl, dimethyloctyl, dimethylcyclohexyl,dimethyldecyl, tri-n-butyl, triamyl, benzyldimethyl, benzyldiethyl,(m-methylbenzyl)diethylamines, or secondary amines such as methyloctyl,ethylamyl, methylcyclohexyl, methylbenzyl, methyldecylamines or primaryamines such as octyl and decyl amines. If desired mixtures of any ofthese amines together or with other amines may be used.

It has been found particularly advantageous to use amines of 9l2 carbonatoms. According to a preferred embodiment of the invention the amine ismethyldibutylamine or tripropylamine.

When the amine/ fatty acid is to be used in conjunction with fungicidallow soluble copper compounds such as the oxychloride, it is preferablenot to use primary alkylamines since these form soluble copper complexesand this tendency is also present, but to a much reduced extent, withsecondary alkylamines. It is therefore preferred in such cases to usetertiary alkylamines.

The higher amines and the fatty acids form solutions when mixedtogether. Thus for example stearic acid forms a homogenous liquidmixture with methyl dibutylamine even when the components are present instoichiometric proportions. The amine may be used in proportions over awide range comprising stoichiometric, or greater or less proportion thanstoichiometric. It is preferred to use the amine in amount comprising100% excess over the stoichiometric equivalent.

The present invention is also for these solutions or salts of saidhigher amines and fatty acids per se as new compositions of matter.These new compositions may be made by mixing the amine and the fattyacid together, suitably for example by dissolving the fatty acid in theamine.

The solution of the amine and the long chain aliphatic acid may beincorporated in the agricultural composition in amounts over a widerange, for example in amount comprising from 1-50% by weight of theweight of the agricultural chemical. It is preferred normally toincorporate the said salt in amount comprising 520% by weight of theweight of the agricultural chemical. Although the solution of the amineand fatty acid may be liquid at room temperature it is normally used insulficiently small amount to make possible its incorporation into awettable powder where the agricultural chemical is a solid. Some of theagricultural chemicals are, however, not capable of absorbing muchliquid material without losing their desirable property of free flow,and in such cases in order to make a satisfactory sprayable wettablepowder it is desirable to include a biologically inert mineral selectedfor its good absorbent properties; such as silica gel, sepiolite orspecial absorbent clays.

When the spray liquid is made up by agitating together in water thesolution of the amine and the long chain aliphatic acid with theagricultural chemical, no other surface active compound is necessary,but the use of such compounds in addition, providing they do notinterfere with the control of evaporation, is permissible. Such furthermaterials may comprise surface active compounds in which the hydrophilicproperty is derived from condensed alkylene oxide, and may for examplebe of the alkylene oxide block polymer type or of the alkyleneoxide-complex type. Surface active agents of the alkylene oxide blockpolymer type which may be mentioned include polypropylene oxide or blockpolymers of ethylene oxide and propylene oxide (such as for example thecommercially available material Pluronic L61). Surface active agents ofthe alkylene oxide-complex type which may be mentioned includecondensation products of ethylene oxide with various hydrophobic hydroxycompounds containing about 530 ethylene oxide units per hydrophobicunit. The hydrophobic unit may comprise for example an alkyl phenol suchas octyl cresol or nonyl phenol (such for example as in thecommeracially available material Lissapol N) or a fatty alcohol such asdodecyl alcohol (such for example as the commercially available materialSersal LAZO) or cetyl alcohol or oleyl alcohol (such for example as thecommercially available material Ethylan O.E.), or the ester of apolyhydric alcohol, for example sorbitol, with a fatty acid. Thesesurface active agents should not be used in amount in excess of theamount required to maintain the composition in a suitable condition forhandling and storage and the use of excess over this amount may resultin interference with the retarding effect on evaporation of thecomposition. It has been found desirable to use the surface activeagents in which the hydrophilic property is derived from condensedalkylene oxide in amount less than 30%, for example 1-30% of the weightof the salt or mixture of the volatile base and aliphatic acid, andpreferably 520% of the weight of the salt or mixture of the volatilebase and aliphatic acid.

The surface active agents of the type indicated while ensuring a stableand fluid suspension do not disturb the retarding effect on evaporationof the salt of a volatile base and a long chain saturated aliphaticcarboxylic acid. Surface active agents of other types can interfere withthe evaporation retardation of the composition.

The salts or mixtures of amine and fatty acids may be solids but areusually liquids at temperatures above about 20-30" C, but at lowertemperatures the latter are frequently of semi-solid or waxyconsistency, and present difficulties in solution in water afterstorage. These disadvantages can be overcome by the addition to the saltor mixture of a solvent in amount sufficient to ensure that the completecomposition is a homogeneous liquid at the lowest temperature at whichit is to be stored or used.

Many organic liquids have some effect in reducing the temperatures belowwhich the amine salts or complexes begin to solidify, and are alsosufficiently soluble in water to avoid the formation of a separateliquid phase when the composition is diluted with water for spraying.These include lower alcohol, glycols, glycol ethers, ketones, esters,glycerol, dioxane, etc., but it has been found that a particularlyeffective group of solvents, as judged by the lowering of thetemperature of solidification of the amine salt or complex obtained witha given proportion of organic liquid comprises the aliphatic alcohols of3, 4 or 5 carbon atoms, preferably with branched chains, when mixed witha suitable proportion of water. In the absence of water the aliphaticalcohols are not good solvents for the amine salts or complexes.

According to a further embodiment the present invention is for a newcomposition of matter comprising a salt or mixture of an amine and afatty acid as defined together with at least one aliphatic alcohol of 3,4 or 5 carbon atoms and water.

The aliphatic alcohol may comprise isopropyl alcohol, normal butylalcohol, secondary butyl alcohol, or secondary amyl alcohol (pentanol-2)or mixtures of'any of these alcohols together or with other alcohols.However it is preferred that the alcohol should comprise a branchedchain compound and according to a preferred embodiment of the inventionthe alcohol is tertiary butyl alcohol, isobutyl alcohol, tertiary amylalcohol or isoamyl alcohol or mixtures thereof.

The volatile base used according to the present invention suitablycomprises an amine which may be a primary,

secondary or tertiary amine and according to a preferred embodiment ofthe invention contains from 616 carbon atoms. Examples of amines whichmay be mentioned include methyldipropyl, tripropyl, methyldibutyl,dimethyloctyl, dimethylcyclohexyl, dimethyldecyl, methyloctyl,methylcyclohexyl and octyl amines.

The following examples are given to illustrate the present invention:

EXAMPLE 1 0.35 pound of stearic acid was dissolved with application ofheat in 0.35 pound (100% excess) of methyldibutylamine. The combinedliquid product was added to 8 pounds of water together with 3.5 poundsof finely divided copper oxychloride. On agitating a satisfactory fluidsuspension (1 gallon) was formed which did not gel appreciably onstanding, and did not froth undesirably. This was sprayed through a T8001 jet at 80 pounds per square inch pressure. After falling through 20feet in a temperature of 90 F. and 40% relative humidity, a deposit wasobtained on pea leaves which, after drying for a further hour, was notwashed off by the application of 5 inches of artificial rain. Thissuspension is suitable for application at a rate of 1 gallon per acre.

Purely by way of comparison, a suspension of copper oxy-chloride of thesame concentration but containing 0.1% octyl-phenol polyethylene oxideWetting agent in place of the amine fatty acid mixture was sprayed undersimilar conditions. After falling 20 feet most of the spray arrived as anon-adherent dust. A few larger drops were collected but were washed oifeasily on application of artificial rain.

EXAMPLE 2 A preparation similar to the above but using 0.175 poundmethyl dibutylamine (stoichiometric equivalent of stearic acid) wassprayed similarly. The deposit obtained on pea leaves consisted ofrather more compact droplets, but was again adherent even after heavyartificial rain.

EXAMPLE 3 As in Example 1 but using 0.2 pound of dimethyl octylamineexcess over stoichiometric equivalence with stearic acid) in place ofmethyl dibutylamine. Tested in the absence of copper oxychloride but inthe same amount of water this product gave a milky solution with onlyminor frothing tendency and rather less viscous than in the case ofmethyldibutylamine. When sprayed with suspended copper oxychloride,deposit was again obtained satisfactorily on the target and, afterdrying, was not washed off by artificial rain.

EXAMPLE 4 As in Example 1 but using 1.94 pounds of copper oxychlorideand 0.49 pound of zinc diethyl dithiocarbamate in place of 3.5 pounds ofcopper oxychloride alone. Reception and retention on pea leaf targetwere again very satisfactory.

EXAMPLE 5 1 pound of palmitic acid was dissolved with the application ofheat in 1 pound of tripropylamine, and the solution was added withpounds of finely ground zinc ethylene bisdithiocarbamate to 13 gallonsof water. The mixture was agitated and formed a satisfactory fluidsuspension which did not gel appreciably on standing nor frothundesirably and which was sprayed through a T 8001 jet at 80 pounds persquare inch pressure. After falling 20 feet in a temperature of 90 F.and 40% relative humidity, a deposit was obtained on pea leaves which,after drying for a further hour, was not washed oif by the applicationof 5 inches of artificial rain. This suspension is suitable forapplication at 1-2 gallons per acre.

Purely by way of comparison, a suspension of Zincethylenebisdithiocarbamate was prepared by adding 20 pounds of finelyground zinc ethylenebisdithiocarbamate with 2 pounds of dodecylalcohol-polyethylene oxide wetting agent and was srpayed under similarconditions. After falling 20 feet most of the spray arrived as anonadherent dust.

EXAMPLE 6 1 pound of arachidic acid was dissolved with the applicationof heat in 0.8 pound of methyldiallyamine and the solution was addedwith 30 pounds of finely ground alphanaphthyl ester of N-methyl carbamicacid to 30 gallons of water. The mixture was agitated and formed asatisfactory fluid suspension which did not gel appreciably on standingnor froth undesirably, and on spraying as indicated in Example 5 formeda deposit which was adherent even after heavy artificial rain.

EXAMPLE 7 1 pound of stearic acid was dissolved with the application ofheat in 075 pound of tripropylamine and the solution was added with 3pounds of finely ground DDT to 4 gallons of water. The mixture wasagitated and formed a satisfactory fluid suspension which did not gelappreciably on standing nor froth undesirably, and on spraying asindicated in Example 5 formed a deposit which was adherent even afterheavy artificial rain.

EXAMPLE 8 1 pound of stearic acid was dissolved in 0.8 pound ofbenzyldimethylamine and the solution was added with 4 pounds of0,0-dimethyl-S-(N-methyl-carbamoylmethyl) phosphorodithioate to 40gallons of water. The mixture was agitated and formed a satisfactoryfluid suspension which did not gel appreciably on standing nor frothundesirably, and on spraying as indicated in Example 5 formed a depositwhich was adherent even after heavy artificial rain.

EXAMPLE 9 1 pound of a 50-50 mixture of stearic acid and palmitic acidwas dissolved in 1 pound of a 50-50 mixture of tripropylamine andtributylamine and the solution was added with a finely ground mixture of6 pounds of sulphur and 12 pounds of copper oxychloride to 5 gallons ofwater. The mixture was agitated and formed a satisfactory solution whichdid not gel appreciably on standing nor froth undesirably, and onspraying as indicated in Example 5 the spray arrived as droplets on theplants. By way of comparison an analagous composition containingoctylphenolpropylene oxide wetting agent in place of the amine fattyacid mixture when sprayed under similar conditions arrived on the plantslargely as dust.

EXAMPLE 10 0.45 pound of stearic acid was dissolved with the applicationof heat in 0.3 pound of methylcyclohexylamine and the solution added to1 gallon of water together with 3.5 pounds of finely divided copperoxychloride. On agitating a satisfactory fluid suspension was obtainedwhich did not gel appreciably on standing nor froth undesirably, and onspraying as indicated in Example 5 formed a deposit which was adherenteven after heavy artificial rain.

EXAMPLE 12 0.35 pound of stearic acid was dissolved with the applicationof heat in 0.35 pound of methyldibutylamine.

The combined liquid product was added to 1 gallon of water together with1 pound of sevin. On agitating a satisfactory fluid suspension wasobtained which did not gel appreciably on standing nor frothundesirably, and on spraying as indicated in Example 5 formed a depositwhich was adherent even after heavy artificial rain.

EXAMPLE l3 Stoichiometric amounts of the amine indicated below andstearic acid were taken, and the stearic acid was dis solved withwarming in the amine and the resulting solution allowed to cool. Theproduct set to a waxy solid or crystalline mass. The melting point ofthe amine stearate was then measured and the results are given below:

Melting point, C. Methyl di-normalpropylamine stearate 23Dimethyl-normalamylamine stearate 31 Dimethyl iso-amylamine stearate 26Di-isobutylamine stearate 41 Di-secondarybutylamine stearate 33Di-normalbutylamine stearate Dimethyl cyclohexylamine stearate 24Methyldibutylamine stearate 21 Methyldi-secondarybutylamine stearate -a23 Dimethyloctylamine stearate 31 Di-isoamylamine stearate 33Di-normalarnylamine stearate 17 Methyl di-normalamylamine stearate 25Dimethyldecylamine stearate 31 Methyl dihexylamine stearate 13 EXAMPLE14 A large number of amine stearates as identified in the followingtable were prepared as described in Example 13. In each case a 1% byWeight solution of the amine stearate in water was prepared, andmillilitres of this solution placed in a 100 millilitre solution andshaken for 1 minute. The height of the froth was measured immediately,and thereafter at time intervals of 10, 30, and 120 minutes. The heightof the froth in centimetres is given in the table below:

Solely by way of comparison salts of a number of amines of up to 6carbon atoms were tested in an exactly similar way, and these resultsare given in the lower part of the table below:

Froth level at time interval, minutes Compound Dimethyl isoamylaminestearatc Di-secondary butylamine stearate Di-normalbutylalninestearatenn Nonylamine stearnte D i-isoamylamine stcarate Di-namylaminestearatc Methyldi-n-amylamine stearate Tributylamine stearate Methyldihexylamine stearatc Methyldioctylamine stcarate...

w OOOOOOOOUIC)! Diethylamine stearate 5.5 Triethylamine stearate 4. ODimothyl sceondary butylamine stearate Dimethyl-n-butylamine men we0000000000 8*. sw- MO 000 00060000010 N. 000 000 OOQOOOOOtQbwe we" UG'000 OQOQQQQOOO -N we EXAMPLE 15 Two compositions were made up asfollows:

Composition B Methyl dibutylamine 0.0 Stearic acid 1.1 Theoleylalcohol-polyethylene oxide condensation product sold as Ethylan O.E0.3

In each case the composition was stirred into about 20 litres of waterand 16 kilograms of copper oxychloride were added with further agitationand the total volume made up to 67 litres with further water.

Subsequently each of preparations from compositions A and B weretransferred to the spray tank of a helicopter adapted to spray through T8002 jets at pounds per square inch pressure (5.5 kilograms per squarecentimetre) and was sprayed at the rate of 1 gallon/ acre (4.54litres/hectare) over a crop of potatoes. The spray dcposited by eachpreparation containing composition A or composition B gave a densecoverage of the leaves and was not washed 01f by running water.

Solely by way of comparison the following compositions were made:

Composition C Kg. Methyl dibutylamine 0.8 Stearic acid 1.1 Sulphite lye1.0

Composition D Methyl dibutylamine 0.8 Stearic acid 1.1 Sodium dodecylsulphate 0.3

Each of compositions C and D were incorporated in preparations inexactly the same way as for compositions A and B. In each case theresulting preparations were sprayed exactly as described above and underthe same conditions and it was found that with the preparationsincorporating each of composition C and composition D only a very lightcoverage of the leaves with spray deposit was obtained and that this wasreadily washed 01f with running water.

EXAMPLE 16 2 pounds of stearic acid were dissolved in 1.3 pounds ofmethyldibutylamine with application of heat. The combined liquid productwas mixed with 1.6 pounds of tertiary butyl alcohol and 3.9 pounds ofwater. The resulting solution was fluid and homogenous at temperaturesdown to 2 C. When added to 80 pounds of water the solution was clear,and when 35 pounds of copper oxychloride were stirred into this dilutedsolution a satisfactory fluid suspension resulted.

The combined liquid product of the stearic acid and the methyldibuylamine alone began to deposit solid when cooled to 19 C., and wascompletely solid at 10 C. The solid product dissolved only withdifliculty in water at 15 C.

EXAMPLE 17 A composition of the same type as described in Example 1contained 2 pounds of stearic acid, 1.3 pounds of methyldibutylamine,1.7 pounds of isopropyl alcohol and 3.3 pounds of water. The resultingsolution remained fluid and homogeneous at temperatures down to 5 C. andwas easily dilutable with water.

EXAMPLE 18 A solution was made from 2 pounds of stearic acid, 1.3 poundsof methyldibutylamine, 1.7 pounds of isoamyl alcohol and 1 pound ofwater. The solution was fluid and homogeneous at temperatures down to 0C., and was easily dilutable with water.

Solely by way of comparison analogous solutions were prepared butincluding 1.7 pounds of the solvent listed in column 1 of the tablebelow in place of isoamyl alcohol. The solidification temperature of thesolution is given in column 2 of the table below. It will be noted thatsolidification occurred in all cases at temperatures over 9 C., whichmay be met in storage conditions.

EXAMPLE 19 3.3 pounds of a solution of stearic acid in an equal Weightof methyldibutylamine, and 0.52 pounds of the octylcresol polyethyleneoxide condensation product sold as Lissapol NX were dissolved in gallonsof water to which was added with agitation an intimate mixture of 19.4pounds of copper oxychloride and 6.3 pounds of technical manganeseethylene bis difihiocarbamate (80% purity).

This mixture was sprayed at 2 gallons per acre through T 8002 jets at 80pounds per square inch pressure and gave a deposit adhering strongly tothe leaves of a banana crop which was only partly washed off by theapplication of 12 inches of artificial rain.

We claim:

1. Composition of matter useful in treating plants comprising (1)agricultural pesticidal chemical,

(2) long chain saturated aliphatic carboxylic acid of 14 to 22 carbonatoms, and

(3) an amine selected from the group consisting of alphatic amine offrom 7 to 16 carbon atoms, (lower alkyl) (cyclohexyl) amine of from 7 to16 carbon atoms, (di-lower alkyl) (cyclohexyl) amine of from 7 to 16carbon atoms, (lower alkyl) (lower alkylphenyl) amine of from 7 to '16carbon atoms, and (di-lower alkyl) (lower alkylphenyl) amine of from 7to 16 carbon atoms, said amine being present in amount comprising 5-100%excess over the stoichiometric equivalent, and said acid and aminecomprising 1-50% by weight of the agricultural chemical.

2. Composition of matter useful in treating plants comprising (l)agricultural pesticidal chemical,

(2) long chain saturated aliphatic carboxylic acid of 14 to 22 carbonatoms, and

(3) methyldibutylamine said methyldibutylamine being present in amountcomprising 5100% excess over the stoichiometric equivalent, and saidacid and methyldibutylamine being present in amount comprising 150% byweight of the agricultural chemical.

3. Composition of matter useful in treating plants comprising (1)agricultural pesticidal chemical,

(2) long chain saturated aliphatic carboxylic acid of 14 to 22 carbonatoms, and

(3) tripropylamine, said tripropylamine being present in amountcomprising 5100% excess over the stoichiometric equivalent, and saidacid and tripropylamine being present in amount comprising 150% byweight of the agricultural chemical.

4. Composition of matter useful in treating plants comprising (l)agricultural pesticidal chemical,

(2) long chain saturated aliphatic carboxylic acid of 14 to 22 carbonatoms,

(3) an amine selected from the group consisting of aliphatic amine offrom 7 to 16 carbon atoms, (lower alkyl) (cyclohexyl) amine of from 7 to16 carbon atoms, (di-lower alkyl) (cyclohexyl) amine of from 10 7 to 16carbon atoms, (lower alkyl) (lower alkylphenyl) amine of from 7 to 16carbon atoms, and (di-lower alkyl) (lower alkylphenyl) amine of from 7to 16 carbon atoms, said amine being present in amount comprising 5100%excess over the stoichiometric equivalent and said acid and aminecomprising 1-50% by weight of the agricultural chemical, (4)saturatedaliphatic alcohol of from 3 to 5 carbon atoms, and (5) water. 5.Composition of matter useful in treating plants comprising 1)agricultural herbicidal chemical, (2) long chain saturated aliphaticcarboxylic acid of 14 to 22 carbon atoms, and (3) an amine selected fromthe group consisting of aliphatic amine of from 7 to 16 carbon atoms,(lower alkyl) (cyclohexyl) amine of from 7 to 16 carbon atoms, (di-loweralkyl) (cyclohexyl) amine of from 7 to 16 carbon atoms, (lower alkyl)(lower alkylphenyl) amine of from 7 to 16 carbon atoms, and (di-loweralkyl) (lower alkyl phenyl) amine of from 7 to 16 carbon atoms, saidamine being present in amount comprising 5100% excess over thestoichiometric equivalent, and said acid and amine comprising 1-5 0% byweight of the agricultural chemical. 6. Composition of matter useful intreating plants com prising (1) agricultural herbicidal chemical, (2)long chain saturated aliphatic carboxylic acid of 14 to 22 carbon atoms,and (3) methyldibutylamine, said methyldibutylamine being present inamount comprising 5l00% excess over the stoichiometric equivalent, andsaid acid and methyldibutylamine being present in amount comprising1-50% by weight of the agricultural chemical. 7. Composition of matteruseful in treating plants comprising (1) agricultural herbicidalchemical, (2) long chain saturated aliphatic carboxylic acid of 14 to 22carbon atoms, and (3) tripropylamine, said tripropylamine being presentin amount comprising 5l00% excess over the stoichiometric equivalent,and said acid and tripropylamine being present in amount comprising 150%by weight of the agricultural chemical. 8. Composition of matter usefulin treating plants comprising (1) agricultural plant growth regulantchemical, (2) long chain saturated aliphatic carboxylic acid of 14 to 22carbon atoms, and (3) an amine selected from the group consisting ofaliphatic amine of from 7 to 16 carbon atoms, (lower alkyl) (cyclohexyl)amine of from 7 to 16 carbon atoms, (di-lower alkyl) (cyclohexyl) amineof from 7 to 16 carbon atoms, (lower alkyl) (lower alkylphenyl) amine offrom 7 to 16 carbon atoms, and (cli-lower alkyl) (lower alkyl phenyl)amine of from 7 to 16 carbon atoms, said amine being present in amountcomprising 5-100% excess over the stoichiometric equivalent, and saidacid and amine comprising 1-5 0% by weight of the agricultural chemical.9. Composition of matter useful in treating plants comprising (1)agricultural plant growth regulant chemical, (2) long chain saturatedaliphatic carboxylic acid of 14 to 22 carbon atoms, and (3)methyldibutylamine, said methyldibutylamine being present in amountcomprising 5-100% excess over the stoichiometric equivalent, and saidacid and methyldibutylamine being present in amount comprising 150% byweight of the agricultural chemical.

11 10. Composition of matter useful in treating plants comprising 1)agricultural plant growth regulant chemical, (2) long chain saturatedaliphatic carboxylic acid of 14 to 22 carbon atoms, and (3)tripropylamine, said tripropylamine being present in amount comprising5-100% excess over the stoichiometric equivalent, and said acid andtripropylamine being present in amount comprising l-50% by Weight of theagricultural chemicalv 11. Composition of matter useful in treatingplants comprising 1) agricultural pesticidal chemical, (2) long chainsaturated aliphatic carboxylic acid of 14 to 22 carbon atoms, and (3) anamine selected from the group consisting of aliphatic amine of from 7 to16 carbon atoms, (lower alkyl) (cyclohexyl) amine of from 7 to 16 carbonatoms, (di-lower alkyl) (cyclohexyl) amine of from 7 to 16 carbon atoms,(lower alkyl) (lower alkylphenyl) amine of from 7 to 16 carbon atoms,and (di-lower alkyl) (lower alkyl phenyl) amine of from 7 to 16 carbonatoms, said acid and amine comprising l-50% by weight of theagricultural chemical. 12. Method for treating plants comprising (1)producing a spray composition by admixing water with (a) agriculturalpesticidal chemical,

(b) long chain saturated aliphatic carboxylic acid of 14 to 22 carbonatoms, and (c) an amine selected from the group consisting of aliphaticamine of from 7 to 16 carbon atoms, (lower alkyl) (cyclohexyl) amine offrom 7 to 16 carbon atoms, (di-lower alkyl) (cyclohexyl) amine of from 7to 16 carbon atoms, (lower alkyl) (lower alkylphenyl) amine of from 7 to16 carbon atoms, and (di-lower alkyl) (lower alkyl phenyl) amine of from7 to 16 carbon atoms, said acid and amine comprising 150% by weight ofsaid agricultural chemical, and (2) spraying said resultant compositionon plants whereby said agricultural chemical is uniformly dispersed andwell adhered on said plants.

References Cited in the file of this patent UNITED STATES PATENTS2,366,013 Duncan Dec. 26, 1944 2,371,289 Hamilton et al Mar. 13, 19452,863,752 Hamm et al Dec. 9, 1958 2,907,691 Hartley et al. Oct. 6, 1959FOREIGN PATENTS 542,725 Canada June 25, 1957 OTHER REFERENCES Bell etal. in Agricultural Chemicals, April 1950, pages 31 to 34, 99 and 101.

1. COMPOSITION OF MATTER USEFUL IN TREATING PLANTS COMPRISING (1) AGRICULTURAL PESTICIDAL CHEMICAL, (2) LONG CHAIN SATURATED ALIPHATIC CARBOXYLIC ACID OF 14 TO 22 CARBON ATOMS, AND (3) AN AMINE SELECTED FRM THE GROUP CONSISTING OF ALIPHATIC AMINE OF FROM 7 TO 16 CARBON ATOMS, (LOWER ALKYL) (CYCLOHEXYL)AMINE OF FROM 7 TO 16 CARBON ATOMS, (DI-LOWER ALKYL) (CYCLOHEXYL) AMINE OF FROM 7 TO 16 CARBON ATOMS, (LOWER ALKYL) (LOWER ALKYLPHENYL) AMINE OF FROM 7 TO 16 CARBON ATOMS, AND (DI-LOWER ALKYL) (LOWER ALKYLPHENYL) AMINE OF FROM 7 TO 16 CARBON ATOMS, SAID AMINE BEING PRESENT IN AMOUNT COMPRISING 5-100% EXCESS OVER THE STOICHIOMETRIC EQUIVALENT, AND SAID ACID AND AMINE COMPRISING 1-50% BY WEIGHT OF THE AGRICULTURAL CHEMICAL. 